CN111303214B - Pyridine tertiary amine iron complex, preparation method thereof and method for catalyzing polymerization of conjugated diene by using same - Google Patents

Pyridine tertiary amine iron complex, preparation method thereof and method for catalyzing polymerization of conjugated diene by using same Download PDF

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CN111303214B
CN111303214B CN202010228691.6A CN202010228691A CN111303214B CN 111303214 B CN111303214 B CN 111303214B CN 202010228691 A CN202010228691 A CN 202010228691A CN 111303214 B CN111303214 B CN 111303214B
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tertiary amine
pyridine
conjugated diene
iron complex
pyridine tertiary
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CN111303214A (en
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王庆刚
王亮
荆楚杨
朱广乾
张献辉
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/02—Iron compounds
    • C07F15/03—Sideramines; The corresponding desferri compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F136/06—Butadiene
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F136/08—Isoprene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/06—Butadiene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/08—Isoprene

Abstract

A pyridine tertiary amine iron complex, a preparation method thereof and a method for catalyzing conjugated diene polymerization by using the pyridine tertiary amine iron complex. The invention belongs to the field of conjugated diene catalytic polymerization. The invention aims to solve the technical problems that the structure of the existing pyridine imine or pyridine amine iron catalyst is easily influenced by a promoter to change, so that the activity and selectivity of the catalyst are reduced, and the heat resistance of the existing iron catalyst is poor. The pyridine tertiary amine iron complex consists of a pyridine tertiary amine ligand and anhydrous FeCl 2 The iron catalyst system is a pyridine tertiary amine iron complex with a definite molecular structure, is simple and easy to obtain in preparation and low in cost, is mainly used for catalyzing the polymerization of conjugated olefins, and has no possibility of reaction between a ligand framework and a cocatalyst compared with the conventional pyridine amine iron catalyst.

Description

Pyridine tertiary amine iron complex, preparation method thereof and method for catalyzing polymerization of conjugated diene by using same
Technical Field
The invention belongs to the field of conjugated diene catalytic polymerization, and particularly relates to a pyridine tertiary amine iron complex, a preparation method thereof and a method for catalyzing conjugated diene polymerization by using the same.
Background
In recent years, more and more attention has been paid to environmentally friendly late transition metal catalyzed olefin polymerizations by scientists. Iron catalysts have also drawn attention in conjugated olefin polymerization because of their environmental friendliness, economy, biocompatibility, and better tolerance to polar monomers.
At present, nitrogen-containing ligands for catalyzing conjugated olefin polymerization by using iron catalysts are mainly pyridine imines or pyridinamines, but skeletons of the two systems are easy to undergo addition reaction or hydrogen extraction reaction under the condition of about a cocatalyst, so that the structure of the catalyst is changed, and the activity and selectivity of the catalyst are further influenced.
Disclosure of Invention
The invention provides a pyridine tertiary amine iron complex, a preparation method thereof and a method for catalyzing polymerization of conjugated diene by using the pyridine tertiary amine iron complex, aiming at solving the technical problems that the structure of the existing pyridine imine or pyridine amine iron catalyst is easily changed by being influenced by a promoter, so that the activity and selectivity of the catalyst are reduced and the heat resistance of the existing iron catalyst is poor.
The invention relates to a pyridine tertiary amine iron complex, which has the structural general formula:
Figure BDA0002428533520000011
wherein R is 1 One selected from methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, benzyl, substituted benzyl, phenyl and substituted phenyl, R 2 One selected from methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, benzyl, substituted benzyl, phenyl and substituted phenyl, R 3 Selected from hydrogen, alkylOr one of the aryl radicals, R 4 One selected from hydrogen, alkyl and aryl.
Further limited, the specific structure of the pyridine tertiary amine iron complex is as follows:
Figure BDA0002428533520000012
Figure BDA0002428533520000021
the preparation method of the pyridine tertiary amine iron complex comprises the following steps: in an anhydrous solvent, pyridine tertiary amine ligand and anhydrous FeCl 2 Mixing, stirring and reacting at 0-60 ℃, and performing post-treatment after the reaction is finished to obtain the pyridine tertiary amine iron complex.
Further defined, the pyridine tertiary amine ligand is reacted with anhydrous FeCl 2 1 is 1.
Further defined, the anhydrous solvent is toluene, tetrahydrofuran, or dichloromethane.
Further defined, the reaction temperature is 25 ℃.
Further limited, the post-treatment steps are, in order: filtering under argon atmosphere, vacuum-pumping, washing with n-hexane until the filtrate is clear, and vacuum-pumping.
Further defined, the pyridine tertiary amine ligand has the structural formula:
Figure BDA0002428533520000022
the invention discloses a method for catalyzing conjugated diene polymerization by using a pyridine tertiary amine iron complex, which comprises the following steps:
under the anhydrous and anaerobic conditions, adding a solvent, a pyridine tertiary amine iron complex, a cocatalyst and a conjugated diene monomer into a reactor in any order, carrying out polymerization reaction for 10min to 6h at the temperature of 0 to 100 ℃, adding a quenching agent after the reaction is finished, and separating and purifying to obtain the poly-conjugated diene.
Further defined, the polymerization temperature is 25 ℃.
Further limited, the solvent is one or a mixture of several of toluene, petroleum ether, pentane and n-hexane in any ratio.
Further defined, the volume ratio of conjugated diene monomer to solvent is 1: (1-20).
Further defined, the volume ratio of conjugated diene monomer to solvent is 2:5.
further defined, the conjugated diene monomer is one or a mixture of two of isoprene and butadiene according to any ratio.
Further defined, when the conjugated diene monomer is a mixture of isoprene and butadiene, the molar ratio of isoprene to butadiene is 1.
Further limiting, a chain transfer reagent is added into the polymerization reaction system, and the chain transfer reagent is allyl chloride, allyl bromide, diethylsilane, triphenylsilane, trimethylsilane, triethylaluminum or triisobutylaluminum.
Further defined, the molar ratio of the chain transfer reagent to the pyridine tertiary amine iron complex is (1-100): 1.
further defined, the molar ratio of the chain transfer agent to the tertiary pyridine amine iron complex is 20.
Further, the molar ratio of the conjugated diene monomer to the pyridine tertiary amine iron complex is (1000 to 20000): 1.
Further defined, the molar ratio of the conjugated diene monomer to the tertiary amine pyridine iron complex is 2000.
Further defined, the cocatalyst is a single component system or a two component system; when the cocatalyst is a single component system, the cocatalyst is methylaluminoxane or modified methylaluminoxane; when the cocatalyst is a two-component system, the cocatalyst is a mixture of an aluminum alkyl and a dealkylating agent.
Further limiting, when the cocatalyst is a single-component system, the molar ratio of the cocatalyst to the pyridine tertiary amine iron complex is (1-1000)): 1.
Further defined, when the cocatalyst is a single component system, the molar ratio of the cocatalyst to the tertiary amine pyridine iron complex is 500.
Further defined, when the cocatalyst is a two-component system, the molar ratio of the alkyl aluminum to the pyridine tertiary amine iron complex is (1-100): 1.
Further defined, when the cocatalyst is a two-component system, the molar ratio of aluminum alkyl to tertiary amine pyridine iron complex is 20.
Further defined, when the cocatalyst is a two-component system, the molar ratio of the dealkylation reagent to the pyridine tertiary amine iron complex is (1-10): 1.
Further defined, when the cocatalyst is a two-component system, the molar ratio of the dealkylating agent to the tertiary amine pyridine iron complex is 1.
Further defined, the alkyl aluminum is trimethyl aluminum, triethyl aluminum, or triisobutyl aluminum.
Further defined, the dealkylating agent is B (C) 6 F 5 ) 3 ，[Ph 3 C][B(C 6 F 5 ) 4 ]Or [ PhNMe 2 H][B(C 6 F 5 ) 4 ]。
Further defined, the feeding sequence is any one of the following three types:
(1) Sequentially adding a cocatalyst, a solvent and a conjugated diene monomer in sequence, and then adding a pyridine tertiary amine iron complex; (2) Sequentially adding a cocatalyst, a solvent and a pyridine tertiary amine iron complex, and then adding a conjugated diene monomer; (3) Adding the pyridine tertiary amine iron complex, the solvent and the conjugated diene monomer in sequence, and then adding the cocatalyst.
Further defined, the quenching agent is a mixed solution of methanol and hydrochloric acid, wherein the volume ratio of methanol to hydrochloric acid is 50.
Further defined, the quencher to solvent volume ratio is 2.
Further, it is to be noted that an aging inhibitor, which is an ethanol solution of 2, 6-di-t-butyl-4-methylphenol at a mass concentration of 1%, may be added after the polymerization is completed.
Further defined, the volume ratio of the aging inhibitor to the solvent is 1.
Further limited, the number average molecular weight of the obtained poly-conjugated diene is 20 to 50 ten thousand, and the molecular weight distribution is 1.8 to 2.0; the cis-1,4 structure accounts for 40-60%, the trans-1,4 structure accounts for 0-15%, and the 3,4 structure accounts for 40-60%.
Further defined, the poly-conjugated diene is primarily used in tire manufacture, especially in the manufacture of automobile tires.
Compared with the prior art, the invention has the following remarkable effects:
1. the iron catalyst system is a pyridine tertiary amine iron complex with a definite molecular structure, is simple and easy to prepare and low in cost, is mainly used for catalyzing the polymerization of conjugated olefins, and has no possibility of reaction between a ligand framework and a cocatalyst compared with the conventional pyridine amine iron catalyst.
2. The poly-conjugated diene obtained by the invention has high molecular weight and narrow molecular weight distribution, and specifically comprises the following components: the number average molecular weight is 20-50 ten thousand, and the molecular weight distribution is 1.8-2.0; the microstructure of the polymer can be regulated and controlled by regulating the structure of the main catalyst, specifically, the cis-1,4 structure accounts for 40-60%, the trans-1,4 structure accounts for 0-15%, and the 3,4 structure accounts for 40-60%.
3. When the iron complex is used as a main catalyst, the activity of the reaction depends on the main catalysts with different substituents and different types of cocatalysts; meanwhile, the catalyst has high activity and good thermal stability in the conjugated olefin polymerization, and has good industrial value.
Drawings
FIG. 1 is a crystal structure diagram of an iron complex of tertiary pyridine amine obtained in accordance with a sixth embodiment.
Detailed Description
The first embodiment is as follows: the structural formula of the pyridine tertiary amine iron complex is as follows:
Figure BDA0002428533520000041
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube is firstly baked for three times, and then 10mL of redistilled dichloromethane and 1.0mmol of anhydrous FeCl are sequentially added into the Schlenk tube 2 And 1.0mmol of pyridine tertiary amine ligand L1, stirring and reacting for 24h at room temperature, after the reaction is completed, filtering under the atmosphere of argon, vacuumizing and drying dichloromethane, washing for 2 times by 10mL redistilled n-hexane until the filtrate is clear, and vacuumizing and drying to constant weight to obtain a yellow solid, namely pyridine tertiary amine iron complex (marked as catalyst 1) (217.2 mg, yield: 83%).
Mass spectrometry analysis: c 16 H 24 Cl 4 Fe 2 N 4: [M-FeCl 2 +H] + : theoretical value: 399.0806; measured value: 399.0807.
elemental analysis: c 16 H 24 Cl 4 Fe 2 N 4 : theoretical value: c,36.54%; h,4.60%; n,10.65%; found C, 36.29%; h,4.88%; n,10.37 percent.
The second embodiment is as follows: the structural formula of the pyridine tertiary amine iron complex is as follows:
Figure BDA0002428533520000051
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube is firstly baked for three times, and then 10mL of redistilled dichloromethane and 1.0mmol of anhydrous FeCl are sequentially added into the Schlenk tube 2 And 1.0mmol of pyridine tertiary amine ligand L2, stirring and reacting for 24h at room temperature, after the reaction is finished, filtering under the atmosphere of argon, vacuumizing to dry dichloromethane, washing for 2 times by 10mL redistilled n-hexane until the filtrate is clear, and vacuumizing to constant weight to obtain yellow solid, namely pyridine tertiary amine iron complex (marked as catalyst 2) (237.8 mg, yield: 82%).
Mass spectrometry analysis: c 20 H 32 Cl 4 Fe 2 N 4: [M-FeCl 3 ] + : theoretical value:419.1665; measured value: 419.1663.
elemental analysis: c 20 H 32 Cl 4 Fe 2 N 4 : theoretical values are as follows: c,41.28%; h,5.54%; n,9.63%; found C,41.02%; h,5.52%; and N,9.55 percent.
The third concrete implementation mode: the structural formula of the pyridine tertiary amine iron complex is as follows:
Figure BDA0002428533520000052
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was first vacuum-baked three times, and then 10mL of redistilled dichloromethane and 1.0mmol of anhydrous FeCl were sequentially added thereto 2 And 1.0mmol of pyridine tertiary amine ligand L3, stirring and reacting for 24 hours at room temperature, after the reaction is finished, filtering under the atmosphere of argon, vacuumizing and drying dichloromethane, washing for 2 times by 10mL redistilled n-hexane until the filtrate is clear, and vacuumizing and drying to constant weight to obtain a yellow solid, namely pyridine tertiary amine iron complex (marked as catalyst 3) (272.2 mg, yield: 81%).
Mass spectrometry analysis: c 28 H 32 Cl 4 Fe 2 N 4: [M-FeCl 3 ] + : theoretical value: 515.1665; measured value: 515.1666.
elemental analysis: c 28 H 32 Cl 4 Fe 2 N 4 : theoretical value: c,49.60%; h,4.76%; n,8.26%; found 49.09% C; h,4.88%; n,8.26 percent.
The fourth concrete implementation mode: the structural formula of the pyridine tertiary amine iron complex is as follows:
Figure BDA0002428533520000061
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube is firstly baked for three times, and then 10mL of redistilled dichloromethane and 1.0mmol of anhydrous FeCl are sequentially added into the Schlenk tube 2 And 1.0mmol of pyridine tertiary amine ligand L4 at room temperatureThe mixture is stirred and reacted for 24 hours, after the reaction is finished, the mixture is filtered under the argon atmosphere, dichloromethane is vacuumized and dried, then 10mL redistilled normal hexane is used for washing for 2 times until the filtrate is clear, and then the mixture is vacuumized and dried to constant weight, so that yellow solid, namely the pyridine tertiary amine iron complex (recorded as catalyst 4), is obtained (302.2 mg, yield: 85%).
Mass spectrometry analysis: c 30 H 36 Cl 4 Fe 2 N 4: [M-FeCl 2 +H] + : theoretical value: 579.1745; measured value: 579.1746.
elemental analysis: c 30 H 36 Cl 4 Fe 2 N 4 : theoretical values are as follows: c,51.03%; h,5.14%; n,7.93%; found C,50.99%; h,5.39%; and N,7.83 percent.
The fifth concrete implementation mode: the structural formula of the pyridine tertiary amine iron complex is as follows:
Figure BDA0002428533520000062
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube is firstly roasted three times by suction, and then 10mL of redistilled dichloromethane and 0.5mmol of anhydrous FeCl are sequentially added into the Schlenk tube 2 And 0.5mmol of pyridine tertiary amine ligand L5, stirring and reacting for 24h at room temperature, after the reaction is finished, filtering under the atmosphere of argon, vacuumizing to dry dichloromethane, washing for 2 times by 10mL redistilled n-hexane until the filtrate is clear, and vacuumizing to constant weight to obtain yellow solid, namely pyridine tertiary amine iron complex (marked as catalyst 5) (176.0 mg, yield: 85%).
Mass spectrometry analysis: c 40 H 40 Cl 4 Fe 2 N 4: [M-Fe 3 ] + : theoretical value: 667.2285; measured value: 667.2283.
elemental analysis: c 40 H 40 Cl 4 Fe 2 N 4 : theoretical value: c,57.86%; h,4.86%; n,6.75%; found C,57.70%; h,4.91%; and N,6.94 percent.
The sixth specific implementation mode: the structural formula of the pyridine tertiary amine iron complex is as follows:
Figure BDA0002428533520000071
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube is firstly baked for three times, and then 10mL of redistilled dichloromethane and 1.0mmol of anhydrous FeCl are sequentially added into the Schlenk tube 2 And 1.0mmol of pyridine tertiary amine ligand L6, stirring and reacting for 24h at room temperature, after the reaction is finished, filtering under the atmosphere of argon, vacuumizing to dry dichloromethane, washing for 2 times by 10mL redistilled n-hexane until the filtrate is clear, and vacuumizing to constant weight to obtain yellow solid, namely pyridine tertiary amine iron complex (marked as catalyst 6) (310.0 mg, yield: 84%).
Mass spectrometry analysis: c 32 H 40 Cl 4 Fe 2 N 4: [M-FeCl 3 ] + : theoretical value: 571.2285; measured value: 571.2286.
elemental analysis: c 32 H 40 Cl 4 Fe 2 N 4 : theoretical value: c,52.35%; h,5.49%; n,7.63%; found C,51.43%; h,5.51%; and 7.27 percent of N.
The seventh embodiment: the application of the pyridine tertiary amine iron complex in catalyzing the polymerization of the conjugated diene is as follows:
to a 25mL Schlenk tube, catalyst 6 (3.67mg, 10 μmol) obtained in accordance with the sixth embodiment, anhydrous toluene (5 mL), isoprene (2.00ml, 20.0 mmol), MAO (5 mmol,500 eq.) were sequentially added under an argon atmosphere, polymerized at 25 ℃ for 120min, and then quenched with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio = 50/1) to obtain an elastomeric polymer.
As a result: yield:>99% number average molecular weight (M) n )：2.7×10 5 Molecular weight distribution (PDI): 2.0. the proportion of different structures: the cis-1, 4-structure accounted for 44%, and the 3, 4-structure accounted for 56%.
The specific implementation mode is eight: the seventh embodiment is different from the seventh embodiment in that: the polymerization time is 10min, and other steps and parameters are the same as those of the seventh embodiment.
As a result: yield:>99% number average molecular weight (M) n )：3.0×10 5 Molecular weight distribution (PDI): 1.9. the proportion of different structures: the cis-1, 4-structure accounted for 45%, and the 3, 4-structure accounted for 55%.
The specific implementation method nine: the application of the pyridine tertiary amine iron complex in catalyzing the polymerization of the conjugated diene is as follows:
to a 25mL Schlenk tube, catalyst 6 (3.67mg, 10 μmol) obtained in accordance with the sixth embodiment, anhydrous toluene (5 mL), isoprene (10.00ml, 100.0 mmol), MAO (5 mmol,500 eq.) were sequentially added under an argon atmosphere, polymerized at 25 ℃ for 10min, and then quenched with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio = 50/1) to obtain an elastomeric polymer.
As a result: yield: 58% number average molecular weight (M) n )：3.8×10 5 Molecular weight distribution (PDI): 1.9. the proportion of different structures: the cis-1, 4-structure accounted for 45%, and the 3, 4-structure accounted for 55%.
The specific implementation mode is ten: the application of the pyridine tertiary amine iron complex in catalyzing the polymerization of the conjugated diene is as follows:
to a 25mL Schlenk tube, catalyst 6 (3.67mg, 10 μmol) obtained in accordance with the sixth embodiment, anhydrous toluene (5 mL), isoprene (2.00ml, 20.0 mmol), MAO (3 mmol, 300 eq.) were sequentially added under an argon atmosphere, polymerized at 25 ℃ for 10min, and then quenched with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio = 50/1) to obtain an elastomeric polymer.
As a result: yield: 96% number average molecular weight (M) n )：2.5×10 5 Molecular weight distribution (PDI): 2.0. the proportion of different structures: the cis-1, 4-structure accounts for 42%, the trans-1, 4-structure accounts for 5%, and the 3, 4-structure accounts for 53%.
The concrete implementation mode eleven: the application of the pyridine tertiary amine iron complex in catalyzing the polymerization of the conjugated diene is as follows:
to a 25mL Schlenk tube under an argon atmosphere, catalyst 6 (3.67mg, 10 μmol) obtained in accordance with the sixth embodiment, anhydrous toluene (5 mL), isoprene (2.00ml, 20.0 mmol), MAO (2 mmol, 200 eq.) were sequentially added, polymerized at 25 ℃ for 10min, and then quenched with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio = 50/1) to obtain an elastomeric polymer.
As a result: yield: 92% number average molecular weight (M) n )：4.0×10 5 Molecular weight distribution (PDI): 1.9. the proportion of different structures: the cis-1, 4-structure accounts for 42%, the trans-1, 4-structure accounts for 6%, and the 3, 4-structure accounts for 52%.
The specific implementation mode twelve: the application of the pyridine tertiary amine iron complex in catalyzing the polymerization of the conjugated diene is as follows:
to a 25mL Schlenk tube, catalyst 6 (3.67mg, 10 μmol) obtained in accordance with the sixth embodiment, anhydrous toluene (5 mL), isoprene (2.00ml, 20.0 mmol), MAO (5 mmol,500 eq.) were sequentially added under an argon atmosphere, polymerized at 70 ℃ for 10min, and then quenched with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio = 50/1) to obtain an elastomeric polymer.
As a result: yield:>99% number average molecular weight (M) n )：1.4×10 5 Molecular weight distribution (PDI): 2.0. the proportion of different structures: the cis-1, 4-structure accounts for 41%, the trans-1, 4-structure accounts for 9%, and the 3, 4-structure accounts for 50%.
The specific implementation mode thirteen: the present embodiment is twelve different from the specific embodiment in that: the polymerization temperature was 100 ℃ and other steps and parameters were the same as those of the twelfth embodiment.
As a result: yield: 90% number average molecular weight (M) n )：1.5×10 5 Molecular weight distribution (PDI): 2.0. the proportion of different structures: cis-1, 4-structure accounts for 40%, trans-1, 4-structure accounts for 13%, and 3, 4-structure accounts for 47%.
The specific implementation mode fourteen are as follows: the application of the pyridine tertiary amine iron complex in catalyzing the polymerization of the conjugated diene is as follows:
to a 25mL Schlenk tube, catalyst 6 (3.67mg, 10 μmol) obtained in accordance with the sixth embodiment, anhydrous toluene (5 mL), isoprene (2.00ml, 20.0 mmol), MMAO (5 mmol,500 eq.) were sequentially added under an argon atmosphere, polymerized at 25 ℃ for 10min, and then quenched with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio = 50/1) to obtain an elastomeric polymer.
As a result: yield:>99% number average molecular weight (M) n )：2.4×10 5 Molecular weight distribution (PDI): 2.0. the proportion of different structures: the cis-1, 4-structure accounted for 47%, and the 3, 4-structure accounted for 53%.
The concrete implementation mode is fifteen: the present embodiment is different from the specific embodiment in the fourteenth aspect: the cocatalyst is DMAO, and other steps and parameters are the same as those of the fourteen specific embodiments.
As a result: yield:>99% number average molecular weight (M) n )：2.9×10 5 Molecular weight distribution (PDI): 2.0. the proportion of different structures: the cis-1, 4-structure accounted for 47%, and the 3, 4-structure accounted for 53%.
The specific implementation modes are sixteen: the application of the pyridine tertiary amine iron complex in catalyzing the polymerization of the conjugated diene is as follows:
to a 25mL Schlenk tube, catalyst 1 (2.61mg, 10 μmol) obtained in the first embodiment, anhydrous toluene (5 mL), isoprene (2.00ml, 20.0 mmol), MAO (5 mmol,500 eq.) were added in this order under an argon atmosphere, polymerized at 25 ℃ for 2h, and then quenched with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio = 50/1) to obtain an elastomeric polymer.
As a result: yield: 37% number average molecular weight (M) n )：2.3×10 5 Molecular weight distribution (PDI): 2.3. the proportion of different structures: the cis-1, 4-structure accounts for 44%, the trans-1, 4-structure accounts for 17%, and the 3, 4-structure accounts for 39%.
Seventeenth embodiment: this embodiment is sixteen different from the specific embodiments in that: catalyst 2 (2.91mg, 10. Mu. Mol) obtained in example two, and the other steps and parameters were the same as those in example sixteen.
As a result: yield: 55% number average molecular weight (M) n )：3.3×10 5 Molecular weight distribution (PDI): 1.8. the proportion of different structures: the cis-1, 4-structure accounts for 44%, and the 3, 4-structure accounts for 5%6％。
The specific implementation mode is eighteen: this embodiment is sixteen different from the specific embodiment: the catalyst was catalyst 3 (3.38mg, 10. Mu. Mol) obtained in the third embodiment, and other steps and parameters were the same as those of the sixteenth embodiment.
As a result: yield:>99% number average molecular weight (M) n )：4.3×10 5 Molecular weight distribution (PDI): 1.8. the proportion of different structures: the cis-1, 4-structure accounted for 37%, and the 3, 4-structure accounted for 63%.
The specific implementation modes are nineteenth: this embodiment is sixteen different from the specific embodiment: catalyst 4 (3.51mg, 10. Mu. Mol) from embodiment four, with the other steps and parameters identical to those of embodiment sixteen.
As a result: yield: 55% number average molecular weight (M) n )：3.6×10 5 Molecular weight distribution (PDI): 1.8. the proportion of different structures: the cis-1, 4-structure accounted for 40%, and the 3, 4-structure accounted for 60%.
The specific implementation mode twenty: this embodiment is sixteen different from the specific embodiment: the catalyst was catalyst 5 (4.14mg, 10. Mu. Mol) obtained in the fifth embodiment, and the other steps and parameters were the same as those in the sixteenth embodiment.
As a result: yield: 77% number average molecular weight (M) n )：3.1×10 5 Molecular weight distribution (PDI): 2.0. the proportion of different structures: the cis-1, 4-structure accounted for 42%, and the 3, 4-structure accounted for 58%.
The specific implementation mode is twenty one: the application of the pyridine tertiary amine iron complex in catalyzing the polymerization of the conjugated diene is as follows:
to a 25mL Schlenk tube under an argon atmosphere, catalyst 1 (2.61mg, 10. Mu. Mol) obtained in the first embodiment, anhydrous toluene (5 mL), triisobutylaluminum (200. Mu. Mol) were added in this order, stirred for 2min, and then a boron salt [ Ph ] was added 3 C][B(C 6 F 5 ) 4 ](10. Mu. Mol), stirred for 2min, added isoprene (2.00mL, 20.0 mmol), polymerized at 25 ℃ for 2h, and then quenched with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio = 50/1) to giveCrosslinking the cyclized product.
As a result: yield: 50% number average molecular weight (M) n )：1.9×10 5 Molecular weight distribution (PDI): 3.4. the proportion of different structures: the cis-1, 4-structure accounts for 42%, the trans-1, 4-structure accounts for 5%, and the 3, 4-structure accounts for 53%.
Specific embodiment twenty-two: the application of the pyridine tertiary amine iron complex in catalyzing the polymerization of the conjugated diene is as follows:
to a 25mL Schlenk tube under an argon atmosphere, catalyst 6 (3.67mg, 10 μmol) obtained in the sixth embodiment, anhydrous toluene (5 mL), allyl chloride (200 μmol), isoprene (2.00ml, 20.0 mmol), MAO (5 mmol, 500eq.) were sequentially added, polymerized at 25 ℃ for 10min, and then quenched with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio = 50/1) to obtain an elastomeric polymer.
As a result: yield:>99% number average molecular weight (M) n )：1.8×10 5 Molecular weight distribution (PDI): 2.5. the proportion of different structures: the cis-1, 4-structure accounted for 46%, and the 3, 4-structure accounted for 54%.
Specific embodiment twenty-three: the application of the pyridine tertiary amine iron complex in catalyzing the polymerization of the conjugated diene is as follows:
to a 25mL Schlenk tube, catalyst 6 (3.67mg, 10 μmol) obtained in the sixth embodiment, anhydrous toluene (5 mL), butadiene (1.75ml, 20.0 mmol), MAO (5 mmol,500 eq.) were sequentially added under an argon atmosphere, polymerized at 25 ℃ for 10min, and then quenched with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio = 50/1) to obtain an elastomeric polymer.
As a result: yield:>99% number average molecular weight (M) n )：4.6×10 5 Molecular weight distribution (PDI): 1.9. the proportion of different structures: the cis-1, 4-structure accounted for 50%, the 1, 2-structure accounted for 50%.
Twenty-four specific embodiments: the application of the pyridine tertiary amine iron complex in catalyzing the polymerization of the conjugated diene is as follows:
to a 25mL Schlenk tube under argon atmosphere, catalyst 6 (7.34mg, 20. Mu. Mol) obtained in accordance with the sixth embodiment, anhydrous toluene (5 mL), isoprene (2 mL,20.0 mmol) and butadiene (1.75 mL,20.0 mmol), MAO (5 mmol, 500eq.), were sequentially added, polymerized at 25 ℃ for 10min, and then quenched with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio = 50/1) to obtain an elastomeric polymer.
As a result: yield:>99% number average molecular weight (M) n )：2.6×10 5 Molecular weight distribution (PDI): 2.3. the proportion of different structures: isoprene: butadiene = 1; isoprene segment: cis-1, 4-structure 42%, trans-1, 4-structure 5%,3, 4-structure 53%; butadiene segment: the cis-1, 4-structure accounted for 48%, and the 1, 2-structure accounted for 52%.

Claims (5)

1. A method for catalyzing conjugated diene polymerization by using a pyridine tertiary amine iron complex is characterized in that the specific structure of the pyridine tertiary amine iron complex is as follows:
Figure FDA0003858318120000011
the method comprises the following steps: under the anhydrous and anaerobic conditions, adding a solvent, a pyridine tertiary amine iron complex, a cocatalyst and a conjugated diene monomer into a reactor in any order, carrying out polymerization reaction at 70-100 ℃ for 10 min-6 h, adding a quenching agent after the reaction is finished, and separating and purifying to obtain the poly-conjugated diene;
the preparation method of the pyridine tertiary amine iron complex comprises the following steps: in an anhydrous solvent, a pyridine tertiary amine ligand and anhydrous FeCl 2 Mixing, stirring and reacting at 0-60 ℃, and performing post-treatment after the reaction is finished to obtain a pyridine tertiary amine iron complex;
the number average molecular weight of the obtained poly-conjugated diene is 20-50 ten thousand, and the molecular weight distribution is 1.8-2.0; the cis-1,4 structure accounts for 40-60%, the trans-1,4 structure accounts for 0-15%, and the 3,4 structure accounts for 40-60%.
2. The method for catalyzing polymerization of conjugated diene by using the pyridine tertiary amine iron complex according to claim 1, wherein the solvent is one or a mixture of toluene, petroleum ether, pentane and n-hexane; the volume ratio of the conjugated diene monomer to the solvent is 1: (1-20).
3. The method for catalyzing the polymerization of conjugated diene through the iron-pyridine tertiary amine complex according to claim 1, wherein the conjugated diene monomer is one or a mixture of isoprene and butadiene; when the conjugated diene monomer is a mixture of isoprene and butadiene, the molar ratio of isoprene to butadiene is 1; the molar ratio of the conjugated diene monomer to the pyridine tertiary amine iron complex is (1000-20000) 1.
4. The method for catalyzing the polymerization of the conjugated diene through the iron pyridine tertiary amine complex according to claim 1, wherein a chain transfer reagent is further added into a polymerization reaction system, and the chain transfer reagent is allyl chloride, allyl bromide, diethylsilane, triphenylsilane, trimethylsilane, triethylaluminum or triisobutylaluminum; the molar ratio of the chain transfer reagent to the pyridine tertiary amine iron complex is (1-100): 1.
5. the method for catalyzing the polymerization of conjugated diene by using the iron pyridine tertiary amine complex as claimed in claim 1, wherein the cocatalyst is a single-component system or a two-component system; when the cocatalyst is a single component system, the cocatalyst is methylaluminoxane or modified methylaluminoxane; when the cocatalyst is a two-component system, the cocatalyst is a mixture of aluminum alkyl and dealkylation reagent; when the cocatalyst is a single-component system, the molar ratio of the cocatalyst to the pyridine tertiary amine iron complex is (1-1000) to 1; when the cocatalyst is a two-component system, the molar ratio of the alkyl aluminum to the pyridine tertiary amine iron complex is (1-100): 1, and the molar ratio of the dealkylation reagent to the pyridine tertiary amine iron complex is (1-10): 1; the alkyl aluminum is trimethyl aluminum, triethyl aluminum or triisobutyl aluminum; said dealkylationThe reagent is B (C) 6 F 5 ) 3 ，[Ph 3 C][B(C 6 F 5 ) 4 ]Or [ PhNMe 2 H][B(C 6 F 5 ) 4 ]。
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